Fuel oil composition



3,198,613 FUEL GIL CGMPGEiITIUN John H. Udelhofen, Glenwood, 111.,assignor to Standard Gil Company, Chicago, 11]., a corporation ofIndiana No Drawing. Filed Aug. 20, 1962, Ser. No. 21%,116 11 Ciaims.(Cl. 4-4-71) This application is a continuation-in-part of Serial No.26,944, filed May 5, 1960, now abandoned.

This invention relates to distillate heating oil compositions containingstabilizers. More particularly, this invention relates to distillatefurnace or heater oil composition containing addition agents capable ofimparting oxidation stability to the distillate furnace or heater oil.

Heating oil compositions are those used for heating purposes such ashome and industrial heating by furnaces, burner heaters and the like. Instorage of distillate heating oil compositions there arises a seriousproblem of inhibiting oxidative deterioration of the oil under storageconditions. The deterioration of distillate heating oils throughoxidation under conditions of storage manifest itself in the appearanceof darker colors, sediment, etc. in the oil. Sediment formation is oftenthe most troublesome problem with which formulators of heating oilblends are concerned because sediment formation normaliy may result inclogging of furnace system equipment such as filters, screens, nozzles,burners, etc., with sludge formed from sediment. The deterioration ofheating oils is much more prevalent Where the oil contains crackedmaterials and because of recent tendencies to blend heating oils bymixing virgin oil fractions with cracked components, oxidativedeterioration has become a problem associated with many commercialblends. The oxidative deterioration problem has, therefore, attractedmuch study and many addition agents have been proposed for stabilizingheating oils.

1 have now discovered new addition agents having exceptionally goodutility in low concentrations in distillate heating oil compositions asstabilizers. The addition agent of this invention is an oil-solublebetaine or a quaternary ammonium salt and corresponds to the structuralformula:

H X to C O- linkage. Where R has more than one carbon atom, any othercarbon atoms of the R group are connected to the one carbon atom as sidechains with respect to the chain. Such linkage is definitive of allalkylidene groups hereinafter which are directly linked to both aquaternary ammonium nitrogen atom and a 3,198,033 Patented Aug, 3, 1965The distillate heating oil composition of this invention comprises adistillate heating oil containing from about 0.000l to about 5 Weightpercent, and more advantageously between 0.0001 and 0.1 weight percent,of the betaines defined herein. The preferred distillate heater oilcomposition of this invention contains the betaine in an amount of fromabout 0.001 to about 0.05 weight percent. The betaines may also beformulated in addition agent concentrates in a suitable organic solventas is more particularly described below.

if the betaine used has low solubility in the distillate oil, solventssuch as aromatic hydrocarbons and alcohols may be used in sufiicientamounts to solubilize the betaine.

In addition to functioning as stabilizers, the betaines used herein mayalso function in distillate heating oil media as rust inhibitors,anti-static agents, dispersants and corrosion inhibitors.

The betaine intended herein may also be called an alkylidene-carboxybetaine of an aliphatic tertiary amine, which betaine contains at leastone substituent group selected from the class consisting of amino andmetal carboxylate, wherein the alkylidene group contains from 1 to 7carbon atoms.

The metals of the metal carboxylate group herein are the metals selectedfrom the class consisting of alkali metals and alkaline earth metals.Examples are sodium, potassium, lithium, barium, calcium and strontium.

referred are sodium, potassium, barium and calcium because of theiravailability.

With reference again to the above formula, the betaines of thisinvention, more particularly, may advantageously contain from about 20to about 55 carbon atoms. The alkylidene group (R) may moreadvantageously contain from 1 to about 4 carbon atoms and preferably isa methylene group.

It is understood that his compounds of the herein described betaines,such as those bis compounds wherein the quaternary ammonium nitrogenatoms are linked through an alkylene group, are also intended.

The aliphatic tertiary amine component group of the above structurecontains the quaternary ammonium nitrogen atom (which contributes theillustrated positive charge) as the tertiary nitrogen atoms of the amineand this nitrogen atom is linked directly through an alkylidene group(R) to the carboxy group (illustrated as having the negative charge).The tertiary amine component roup may be derived from the correspondingtertiary amine.

The tertiary amine component group may be any acyclic hydrocarbontertiary amine group having at least one amino and/or metal carboxylatesubstituent and/ or constituent, i.e., containing an amino and/or metalcarboxylate group.

Usually the betaines may be prepared by reaction of the correspondingtertiary amine with a suitable salt or ester of an wmonohalogenatedaliphatic carboxylic acid. The reaction may be carried out in thepresence of a sol vent such as benzene, ethanol, n-butanol, isopropanol,etc., and in the presence of a promoter such as an inorganic iodide,e.g., potassium iodide. The reaction may conveniently be carried out atthe reflux temperature of the solvent and may take from two to fiftyhours for substantial completion. An acceptable temperature for thereaction may be in the range of from about 50 F. to about 200 F.although higher or lower temperatures a 3 may be used. The reactionproceeds to form a betaine product wherein the portion of the betaine isderived from the ester or salt of the a-monohalogenated aliphaticcarboxylic acid. Thus, the size and configuration of the R (alkylidene)group is determined by the aliphatic group of the monohalogenatedaliphatic carboxylic acid salt or ester and may be pre-selected by anychemist of ordinary skill by selection of the appropriate acid salt orester.

Variations in the above preparation may be useful, desirable or evennecessary in some cases. For example, in the preparation of a betainehaving a metal carboxylate constituent in the tertiary amine componentgroup, it would be impractical to attempt to first prepare the exactcorresponding tertiary amine first because it may readily be prepared insitu during formation of the betaine by reacting a secondary amine withtwice as much of the corresponding metal salt of the monohalogenatedaliphatic carboxylic acid as would normally be used for the equimolaraddition. added and one remains in the form of the metal salt, i.e., asa metal carboxylate group attached to the nitrogen of the secondaryamine to provide the tertiary amine component. Other variations inpreparation will be evident to those skilled in the art, e.g. well knownpreparation technique for obtaining bis compounds. The reactionsinvolved, e.g., acylation, are well known and do not form a part of thisinvention except for obtaining the useful product defined herein.

Two carboxy groups are thereby Examples of salts or esters of theu-monohalogenated aliphatic carboxylic acids which may be used in theabove exemplified procedure of preparation of the betaines of thisinvention are: sodium chloroacetate, sodium bromoacetate, methylchloroacetate, butyl bromoacetate, sodium a-chlorobutyrate, sodiuma-chlorovalerate, methyl a-tbromovalerate, sodium a-chlorocaproate,sodium a-bromocaprylate, isopropyl monobromo butyrate, sodiuma-chloroethylhexanoate, sodium Ot-ChlOYO-dimethyl-valerate, etc. Ofcourse, the corresponding calcium, magnesium, potassium or other saltsmay also be used in lieu of the sodium salts but may be less availableor more expensive.

The substituted aliphatic acyclic tertiary amine betaines useful inaccordance herewith may more particularly be defined by the followingstructural formula:

wherein R is as defined above, at least one of the R groups is an alkylgroup having from 1 to 12, and preferably 1 to 6, carbon atoms andcontaining a snbstituent group selected from the class consisting of anamino group and an alkali or alkaline earth metal carboxylate group, andthe remainder of the R groups are alkyl groups having from 1 to 22carbon atoms and preferably from about 10 to 22 carbon atoms.

Thus, the betaines useable hereinarea class of betaines consisting ofN-(carboxyalkylidene) amino acyclic tertiary amine betaines, and alkaliand alkaline earth metal carboxylate acyclic tertiary amine betaines.

In the nomenclature herein, certain alkyl groups are referred to ascoco, soybean and tallow. Such terms indicate the source of fatty acidsfrom which the alkyl group has been derived, i.e., coconut fatty acids,soybean fatty acids and tallow fatty acids. These groups generally arederived from mixed'C to C fatty acids. The coco groups are derived fromcoconut fatty acids and average about C to C The soybean groups arederived from soybean fatty acids and average about C The tallow groupsused herein are hydrogenated tallow groups derived from tallow fattyacids and average about C and tallow and hydrogenated tallow are usedinterchangeably to describe such groups.

THE N- CARBOXYALKYLIDENE AMINO ACYCLIC TERTIARY AMINE BETAINES TheN-(carboxyalkylidene) amino acyclic tertiary amine betaines useableherein advantageously have the following structural formula: V t

wherein R is an alkylidene group having from 1 to 7 and preferably from1 to 4 carbon atoms, R is an alkyl group having from 1 to 22 andpreferably 10 to 22 carbon atoms, and R is an amino alkyl group havingfrom 1 to about 12 and preferably 1 to 6 carbon atoms.

Bis compounds of the above are also intended and may advantageously havethe following structural formula:

wherein R and R are defined as above, R is R R and R are each selectedfrom R and R and R is an alkylene group having from 2 to 12 andpreferably 2 to 6 carbon atoms.

The betaines of Formula 1 above may be preparedby reacting thecorresponding N,N-dialkyl alkylene diamine, or N,N-dialkyl polyalkylene,triamine, tetramine or pentamine with the salt or ester ofmono-halogenated aliphatic carboxylic acid in about equimolar amounts.The betaines of Formula 2 are bis-compounds and may be prepared in thesame manner except that the salt or ester of monohalogenated carboxylicacid is used in an amount 'suflicient to provide two moles per mole ofamine and the amine used is a polyalkylene polyamine, e.g., a polyaminoacyclic tertiary amine betaines are: N-(carboxy methylene) N-aminopropylN,N-di(hydrogenated tallow) amine betaine, N-(carboxy 2-butylidene)N-aminoheptyl N,N-dicoco amine betaine, N-(carboxy 2-propylidene)N-aminopropyl N,N-dioleyl amine betaine, N-(carboxy 3-hexylidene)N-aminohexyl N,N-dihexecosyl amine betaine, N-(carboxymethylene)N-aminomethyl N,N-di-' soybean amine betaine, N-(carboxymethylene)N-aminododecyl N,N-dihexyl amine betaine, N-(carboxymethylene)N-aminododecyl N,N-dimethyl amine betaine, N- (carboxymethylene)N-aminoisooctyl N,N-diisoocty1 amine betaine, N-(carboxymethylene)N-aminopropyl N,N-di(hydrogenated tallow) amine betaine,N-(carboxy-methylene) N-aminopropyl N,N-dicoco amine be- More examples,with reference to Formula 2 above, i.e., bis compounds, are as definedbelow with respect to component groups of the Formula 2 defined above:

6 ance herewith, is prepared by reacting 6.5 grams of N,N- ditallowtetraethylene pentamine with 1.0 gram of sodium chloroacetate in thepresence of one crystal of K1 Example R1 R R3; Rab R30 R4 a MethyleneEicosyl 3-aminopropyl 3-aminopropy1. 3-aminopropyl Propylene. bl-butylidene Tallow TaLow Tallow .a o Do. 0. 1-hexylidene I-lexaclecyl-2-aminoethyl Hexadecyl. Ethylene. cl. l-propylidene Octadecyl 0Octadecyl o. e. 2-heptylidene Dodeeyl Aminododecyl Dodeeyl Dodecylene.f- Methylene do Methyl Do.

Aminohexyl Octyl. Hexylene. Aminodecyk. "do Decylene. Zarninoethyl.Zaminoeth Ethylene. do Stearyl o. Do.

3-aminopropyl Coco 3-aminopropyl Propylene. r do Z-aminoothyk-2-aminoethyl Ethylene.

do Hexadecyl 3-aminopropyl Propylene. do "lallo Do.

do. Ethylene. .do- Propylene. .do I D 0. .do Do. 2-nminoethyl. Ethylene..do D0.

Example of Preparation (I) The N-(carboxymethylene) N-(3-aminopropyl)N,N- ditallow amine betaine, useable in accordance herewith, is preparedby reacting 5.94 grams of N,N-ditallow 1,3- propylene diamine (marketedas Duom en ZHT) With 1.2 grams of sodium chloroacetate in the presenceof one crystal of potassium iodide (catalyst) in 30 ml. of nbutanolsolvent for 24 hours at the reflux temperature of the solvent. Themixture is then filtered to remove solids and the final product isseparated from the filtrate as a semi-solid by vacuum distilling toremove solvent. The yield of product is 6 grams.

Example of Preparation (11) The N-(carboxy l-butylidene)N-ethylaminoethyl N- ethyl N-decyl amine betaine, useable in accordanceherewith, is prepared by reacting 5.1 grams of N-decyl triethylenediamine with 3.1 grams of methyl a-chlorovalerate in the presence of onecrystal of potassium iodide (catalyst) in 50 ml. of n-butanol solventfor 16 hours at the reflux temperature of the solvent. The mixture isthen filtered to remove solids and the final product is separated fromthe filtrate as a semi-solid by vacuum distilling to remove solvent.

Example 0 Preparation (III) The N',N,N"-tristearyl N"-ethylaminoethylN',N"-di- (carboxymethylene) ethylene diamine betaine, useable inaccordance herewith, is prepared by reacting 4.5 grams ofN',N,N"-tristearyl triethylene triamine (may be derived from stearicacid and triethylene triamine) with 1.2 grams of sodium chloroacetate inthe presence of one crystal of K1 (catalyst) in 100 ml. of n-butanolsolvent for 20 hours at the refiux temperature of the solvent. Themixture is then filtered to remove solids and the final product isseparated from the filtrate as a semi-solid by vacuum distilling toremove solvent.

xample of Preparation (IV) The N-(carboxymethylene) N-tallow N-methyl N-aminopropyl amine betaine, useable in accordance here With, is preparedby reacting 5.2 grams of N-tallow N- methyl 1,3-propylene diamine with1.5 grams of sodium chloroacetate in the presence of one crystal of K1(catalyst) in 50 ml. of n-butanol solvent for 24 hours at the refluxtemperature of the solvent. The mixture is then filtered to removesolids and the final product is separated from the filtrate as asemi-solid by vacuum distilling to remove solvent.

Example of Preparation (V) The N-(carboxymethyl) N,N-ditallowN-aminoethylaminoethylaminoethyl amine betaine, useable in accord-(catalyst) in ml. of isopropanol solvent for 30 hours at the refluxtemperature of the solvent. The mixture is then filtered to removesolids and the final product is separated from the filtrate as asemi-solid by vacuum distilling to remove solvent.

THE N-(CARBOXYALKYLIDENE) ALKALI AND ALKALINE EARTH METAL CARBOXYLATEACYCLIC TERTIARY AMINE BETAINES The N-(carboxyalkylidene) alkali andalkaline earth metal carboxylate acyclic tertiary amine betaines useableherein advantageously have the following structural formula:

wherein R is an alkylidene group having from 1 to 7 and preferably from1 to 4 carbon atoms, R is an alkyl group having from 1 to 22 andpreferably 10 to 22 carbon atoms, M is a metal selected from the classconsisting of alkali and alkaline earth metals and n is an integer offrom I to 2 inclusive and corresponds with the valence of said metal.

The betaines of Formula 3 above may be prepared by reacting thecorresponding dialkyl amine with the salt or ester or monohalogenatedaliphatic carboxylic acid in amounts providing at least about two molesof the salt or ester per mole of dialkyl amine in the reaction mixtureand neutralizing the resulting product with a molar excess of basic ahall or alkaline earth metal compound. Neutralization is carried outduring the reaction of the amine and salt or ester by adding the basicalkali or alkaline earth metal compound to the reaction mixture.Examples of suitable alkali and alkaline earth metal compounds are:NaHCO KHCO Na CO BaO, NaOH, KOH, CuO, BaS, SrO, LrOF-l, etc.

Specific examples of useable N-(carboxyalkylidene) alkali and alkalineearth metal carboxylate acyclic tertiary amine betaines are:

N- carb oxymethylene) N,l l-ditallow N- (sodium carboxyrnethylene) aminebetaine,

N-(carboxy l-hexylene) N,Ndidodecyl N-(potassium carboxymethylene) aminebetaine,

N-(carboxymethylene) N,N-dihexadecyl N-(lithium carboxypropylene) aminebetaine,

barium di-{5-[N,N-ditallow 'N-(carboxy 2-butylidene) amino]valerate}betaine,

calcium di-{Z-[NN-didecyl N-(carboxymethylene) amino] acetate}betaine,

strontium di-{2-[N,Ndistearyl N-carboxymethylene) example, a heavyindustrial residual fuel (e.g., Bunker C), a furnace oil, a heater oilfraction, kerosene, a gas oil, or any other like light oil intended forfurnace or heater fuel use. Of course, any mixtures of oils are alsointended. The distillate heating oil may be virgin or cracked petroleumdistillate oil. Thedistillate heating f'oiI may advantage boil in therange of frbm about N-(carboxymethylene) N-(sodium carboxymethylene)N,N-dioctyl amine betaine, N-(carboxymethylene) N-(sodiumcarboxymethylene) N,N-diheptadecyl amine betaine f N-(carhoxymethylene)N-(sodium carboxymethylene) N,N-dieicosyl amine betaine,N-(carboxymethylene) N-(sodium carboxymethylene) N,N-dicoco aminebetaine, 7 V N -(carboxymethylene) N-(sodium carboxymethylene)N,N-disoybeanamine betaine, and the like.

Example of Preparation (VI) The N-(sodium carboxymethylene)N-(carboxymethylene) N,N-ditallow amine betaine, useable in accordanceherewith, is prepared by reacting 9.80 grams of ditallow amine (ArmeenZHT marketed by Armour Chemical Div.) with 4.64 grams of sodiumchloroacetate and 5.00 grams of sodium bicarbonate in the presence ofone crystal of KI (catalyst) in 50 ml. of isopropyl alcohol solvent for24 hours at the reflux temperature of the solvent. The mixture is thenfiltered to remove solids and the final product is separated from thefiltrate as a semisolid by vacuum distilling to remove solvent. Theyield of product is 13 grams.

Example of Preparation (VII) The N-(potassium carboxy l-butylidene)N-(carboxy l-butylidene) N,N-didodecyl amine betaine, useable inaccordance herewith, is prepared by reacting 4.1 grams of didodecylamine with 4.1 grams of potassium a-bromovalerate and 5.0 grams ofpotassium bicarbonate in the presence of one crystal of K1 in 50 ml. ofxylene solvent for 32 hours at the reflux temperature of the solvent.The mixture is then filtered to remove solids and the final product isseparated from the filtrate as a semi-solid by vacuum distilling toremove solvent.

Example of Preparation (VIII) The barium di{2-[N-tallow N-methylN-carhoxymethylene amino] acetate}betaine, useable in accordanceherewith is prepared by reacting 7.0 grams of tallow methyl amine with6.0 grams of sodium chloroacetate and 2.0 grams of barium oxide in thepresence of one crystal of K1 in 100 ml. of methanol solvent for 36hours at the reflux temperature of the solvent. The mixture is thenfiltered to remove solids and the final product is separated from thefiltrate as a semi-solid by vacuum distilling to remove solvent.

Example of preparation (IX) The calcium di{2[N,N-dioleylN-(carboxymethylene) amino]acetate}betaine, useable in accordanceherewith is prepared by reacting 8.3 grams of dioleyl amine with 4.0grams of sodium chloroacetate and 0.7 gram of calcium oxide in thepresence of one crystal of K1 in 100 ml. of n-butanol solvent for 20hours at the reflux temperature of the solvent. The mixture is thenfiltered to remove solids and the final product is separated from thefiltrate as a semi-solid by vacuum distilling to remove solvent.

HEATING OIL COMPOSITIONS The above described betaines may be used inaccordance herewith as distillate heating oil stabilizers.

The distillate heating oil in which the betaines are used in accordanceherewith is a hydrocarbon oil, such as for 200 to about 700 F., andpreferably in the range of 350 to 650 F. The distillate oil may'containor consist'of cracked components, such as for "example, those derivedfrom cycle oil or cycle oil cuts boiling heavier than gasoline, usuallyin the range of from about 450 to about 750 F. and may be derived bycatalytic or thermal crack- 7 ing. High-sulfur-containing andlow-sulfur-containing oils may also be used. The distillate 'oil may, ofcourse, contain other components such as addition 'agentsused to performparticular functions. e

The preferred heating oils have an initial boiling point in the range offrom about 350 to about 475 F. and an end pointin the range of fromabout500 to about 650. F. The furnace oil may advantageously have anA.P.I. gravity of about at least 30 and a flash point (Tag closed cup)not lower than about Fgand preferably above about F. V

In order to test the etfectiveness of the betaines as heating oiladdition agents and more particularly as heating oil stabilizers,various samples of heating oil compositions containing the betaines asaddition agents were prepared and tested. Each sample was prepared bymixing the betaine indicated below in very small amounts with a basefurnace oil in amounts described below:

' Base furnace oil.A mixture of 50 vol. percent light catalytic cycleoil and 50 vol. percent virgin gas oil.

Sample A.-Tl1e base furnace oil above containing 0.005 weight percent ofthe N-(carboxymethylene) N-(3- aminopropyl) N,N-ditallow amine betaineprepared as in example of Preparation I.

Sample B.Thebase furnace oil above containing 0.01 weight percent of theN-(sodium carboxymethylene) N- (carboxymethylene) N,N-ditallow aminebetaine, prepared'as in example of Preparation VI.

The above base furnace oil and samples were aged in stoppered containersin the dark at 200 F. for 20 hours and then at room temperature (70 F.)for about 48 hours. The aged base furnace oil and samples were eachsubjected to the following tests with the results reported at the end ofeach test procedure:

Sediment test-100 mgs. of each aged sample was passed through a frittedglass crucible of fine porosity and the insolubles were collected on thecrucible, Washed wtih hexane and the crucible was then evaporated.Weights of 'insolubles collected'from each sample were as follows:

Sample: Mg. of insolubles Base furnace oil 4.6 A 1.4 B 0.5

Sample: Mg. of soluble gum Base furnace oil 37.4 A 18.6 B 14.7

i Filterability test. In this test, 8 successive 50 ml. incre. merits ofeach sample tested are poured through a one (2111. area of 10 paper. Thetime in seconds for each increment was noted. Results were as follows:

Time in Seconds, Each Increment Water flocculation test.The incrementsof filtrate from each of the above filterability tests for each samplewere combined and the total filtrate from each sample was mixed with anequal amount (about 400 ml.) of water. Mixing was accomplished byvigorous shaking. The sample and water mixture was then allowed tosettle for about 5 to minutes until an interfacial rag appeared. Eachmixture was then passed through a medium porosity fritted glasscrucible. The appearance of the mat left in the crucible was noted andrecorded as a measure of the sludge formed by contact with water. Theresults were Emulsification test-In this test, the time in minutesrequired to clear a water-in-oil emulsion (1% water in oil: 3 ml. H O in300 ml. oil) by blowing with a stream of air is determined.

The results were as follows:

Sample: Time in minutes Base furnace oil 11 The results of the abovetest procedures demonstrate the efficiency of the betaines of thisinvention as heating oil stabilizers. With reference to the testresults, the sediment test resuits are a measure of the dispersantproperties and anti-oxidant properties of the betaine addition agents.The very small amounts of insolubles collected demonstrate excellentdispersant properties as well as antioxidant properties. The soluble gumtest is a measure of the anti-oxidant properties of the various samplestested and indicates that the betaines are effective anti-oxidationaddition agents even in very small amounts. The filterability test is ameasure of dispersant properties of the betaines and the data showgreatly improved filterability in comparison with the control. The waterflocculation test determines the sludge inhibiting tendencies of anadditive and the above results demonstrate an improvement in appearanceof the sample compared with the control base furnace oil due to improvedsludge inhibition. The NPA color test is well known and indicates theamount of color degradation of each sample due to the aging process. TheNPA results show good color for the betaine stabilized composition,better than the non-stabilized control. The emulsification test resultsdemonstrate the emulsion stabilizing tendencies of the betaines asfurnace oil addition agents. The emulsions were much more stable thanwas the emulsion in the control furnace oil.

The betaines may, for convenience, be prepared as addition agentconcentrates. Accordingly, the betaine is prepared in or dissolved in asuitable organic solvent therefor in amounts greater than 10% andpreferably from about 25% to about 65%. The solvent in such concentratemay conveniently be present in amounts from about 35% to about 75%. Theorganic solvent preferably boils within the range of from about F. toabout 700 F. The preferred organic solvents are hydrocarbon solvents,for example, petroleum fractions such as naphtha, heater oil, mineralspirits and the like, because of their clean burning properties. Thesolvents selected should, of course, be selected with regard to possiblebeneficial or adverse effects it may have on the ultimate heating oilcomposition. Thus, the solvent should preferably burn without leaving aresidue and should be non-corrosive with regard to metal, and especiallyferrous metals. Other desirable properties are obvious from the intendeduse of the solvent.

All percentages given herein are percentages by weight unless otherwiseindicated.

It is evident from the foregoing that I have provided heating oilcompositions containing defined betaines as multi-purpose additionagents effective in very small amounts.

I claim:

1. A heating oil composition comprising a major amount of distillateheating oil and between 0.0001 and 0.1 weight percent of a betaineselected from the class consisting of a betaine containing at least 20carbon atoms and having the structural formula:

and a his compound thereof, wherein R is an alkylidene group containingfrom 1 to 4 carbon atoms, R is selected from the class consisting of anamino alkyl group, an alkali metal carboxylate group and an alkalineearth metal carboxylate group, R is an alkyl group having from 10 to 22carbon atoms, and R is selected from the class consisting of R and R".

2. The composition of claim 1 wherein said distillate heating oil is amixture of virgin and cracked petroleum distillate heater oils.

3. The composition of claim 2 wherein the cracked component is derivedby cracking a cycle oil boiling heavier than gasoline.

4-. The composition of claim 1 wherein said distillate heating oil boilsin the range of 3 50 to 650 F.

5. The composition of claim 1 wherein R" is derived from hydrogenatedtallow fatty acid.

6. The composition of claim 1 wherein R is a 3-aminopropyl group.

'7. The composition of claim 1 wherein R is a sodium acetate group.

8. The composition of claim 1 wherein R is a methylene group.

9. The composition of claim 1 wherein said betaine has the followingstructural formula:

wherein R is an alkylidene group having from 1 to 4 carbon atoms, R isan alkyl group having from 10 to 22 car bon atoms, and R is an aminoalkyl group having from 1 to 6 carbon atoms.

10. A heating oil composition comprising a major amount of distillateheating oil and between 0.0001 and 0.1 weight percent of a betainehaving the following structural formula:

RICO 1 1 wherein R is an alkylidene group having from 1 to 4 carbonatoms, R is an alkyl group having from to 22 carbon atoms, M is a metalselected from the class consisting of alkali metals and alkaline earthmetals and n is an integer of from 1 to 2 inclusive corresponding to thevalence of said metal.

11. A heating oil composition concentrate containing from about 25% toabout of the betaine of claim 1 and from about 35% to about of ahydrocarbon solvent boiling at a temperature in the range of from aboutF. to about 700 F., said concentrate being capable of dilution with adistillate heating oil to a betaine concentration in the range between0.0001 and O.=1 Weight percent.

DANIEL E.

Shappirio 252-403 Shappirio 252-401 Shappirio 252403 Stayner et al 4471Lew 260501 Vitalis 260501 Bartlett 4466 Ebner 4466 WYMAN, PrimaryExaminer.

1. A HEATING OIL COMPOSITION COMPRISING A MAJOR AMOUNT OF DISTILLATEHEATING OIL AND BETWEEN 0.0001 AND 0.1 WEIGHT PERCENT OF A BETAINESELECTED FROM THE CLASS CONSISTING OF A BETAINE CONTAINING AT LEAST 20CARBON ATOMS AND HAVING THE STRUCTURAL FORMULA